B： gT视雜 五、發明說明（11 ) 福充 ij 混合物依箭號6之方向進料至外層環狀槽65，而該混合物 則經由篩管62進入環狀槽64。同時，強迫母液進入内層 篩管61並經由管線8而排出。通過篩管61及62之流向 係 可藉由同時可換向之閥66及67換向，俾使篩孔阻斷可經 週期性換向而減少，或可藉由管線6或8中所測得之壓力 變化而引發換向而使篩孔阻斷減少。於各例中藉由換向而 發生環狀槽中母液濃度之變化係可在各例中之下游混合容 器中被平均。 圖式中之標號具有下列意義： (請先閱讀背面之注意事項再填寫本頁) — 經濟部智慧財產局員工消費合作社印製 1，31 結晶器 2 冷卻夾套 3，33 冷卻單元 4, 6, 6a, 6b, 8, 9, 11, 17, 19, 21, 34, 41, 48,49, 51 管線 5, 35 交換容器 7, 22, 47 濾器 10，40 混合容器 12 往復泵 13 篩板 14 刮刀 -13 - 訂---------^ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 五、發明説明（】） A7 B7 經濟部中央標準局員工消費合作社印製 本發明係相關於一種用於籍由懸浮結晶而自液態彳b合物混 合物中分離出可結晶有機化合物之方法。 鐘於其合成之方法’一敏有機化合物俾經以化合物混合物 之形式而獲得’其除所需之有機化合物外，尚包含本質上 或具優勢含量之其他化合物，例如溶齊丨i起始化合物、副 產品及/或該有機化合物冬異構物。在許多例子中’該所需 之有機化合物可'藉由結晶而自混合物中分離出。許多寸結 蠤有機化合物之特徵係具有外來物質之低固相溶解度，因 此結晶鏗常荩選擇來用於分離之方法。 先前技藝所習用之方法’係特別在於溶液結晶’或自化合 物混合物本身中靜態結晶消往^^17啦丨1^如11)，其中將該 欲鉸單離之化合物沈積於固定之冷凍表面，然後自母.液中 分離出並再度熔化。 此兩種結晶法均需要利用大量的能暈，因為該欲經冷卻並 ，經再度加熱以角於結蟲之質量相當穩度地超出實螓欲經分 灕之反應物的質量。 一般两言，懸滓液中結晶通常是可在使用較少年能董下進 行’並若以根據美國“A3竹7的2及美國_A3 872 009中， 使用所謂的洗滌塔(Wash： column)進行分離及作為熔融結晶 相時，較之靜態結晶法真有更佳之效率。 3 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ΓΊΙ1.--1 —®裝— I (請先閲請背面之注意事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製 A7 iVi λ:：, S8* 9* 2¾ B7 Ui本年月B: gT as miscellaneous. V. Description of the invention (11) The mixture of Fuchong ij is fed into the outer ring groove 65 in the direction of arrow 6, and the mixture enters the ring groove 64 through the sieve tube 62. At the same time, the mother liquor is forced into the inner screen tube 61 and discharged through the line 8. The flow direction through the sieve tubes 61 and 62 can be reversed by valves 66 and 67, which can be reversible at the same time, so that the sieve block can be reduced by periodic reversal, or can be measured by line 6 or 8. The resulting pressure change causes commutation and reduces screen blockage. In each case, the change in the concentration of the mother liquor in the annular tank by reversal can be averaged in the downstream mixing container in each case. The labels in the diagram have the following meanings: (Please read the precautions on the back before filling out this page) — printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1, 31 mold 2 cooling jacket 3, 33 cooling unit 4, 6 , 6a, 6b, 8, 9, 11, 17, 19, 21, 34, 41, 48, 49, 51 pipeline 5, 35 exchange container 7, 22, 47 filter 10, 40 mixing container 12 reciprocating pump 13 sieve plate 14 Squeegee-13-Order --------- ^ This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) V. Description of the invention ()) A7 B7 Staff consumption of the Central Bureau of Standards, Ministry of Economic Affairs Printed by a cooperative The present invention is related to a method for separating crystallizable organic compounds from a liquid sulfonium compound mixture by suspension crystallization. Zhong Yu's method of synthesis 'a sensitive organic compound is obtained in the form of a compound mixture', which, in addition to the required organic compound, also contains other compounds that are essential or have an advantageous content, such as the starting compound , By-products and / or winter isomers of the organic compound. In many cases, 'the desired organic compound can be isolated from the mixture by crystallization. Many organic compounds are characterized by the low solid-phase solubility of foreign substances, so crystallization is often the method of choice for separation. The method conventionally used in the prior art is 'specially in solution crystallization' or static crystallization from the compound mixture itself ^^ 17 啦 丨 ^^ 11), in which the compound to be isolated is deposited on a fixed frozen surface, It was then separated from the mother liquor and melted again. Both of these crystallization methods require the use of a large amount of energy, because the mass of the reactant that is to be cooled and heated again to stabilize the knotworms steadily exceeds the mass of the reactant that is to be separated. Generally speaking, the crystallization in suspension liquid can usually be carried out with a few years of energy use, and if according to the US "A3 Bamboo 7 2 and US_A3 872 009, the so-called washing column (Wash: column ) For separation and as a molten crystalline phase, it has better efficiency than the static crystallization method. 3 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ΓΊΙ1 .-- 1 —® equipment — I (please (Please read the notes on the back before filling this page)-Order A7 iVi λ ::, S8 * 9 * 2¾ B7 Ui
I ' l7：J " ......... Vi-..'·;; ------- 五、發明說明（） 15 熱交換器 16 閥 17 箭號 18 泵 20 洗滌塔 61, 62，63 管 64，65 環狀槽 66,67 可換向之閥 Μ 馬達 -13-1 - (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）I 'l7: J " ......... Vi-..' · ;; ------- V. Description of the invention () 15 Heat exchanger 16 Valve 17 Arrow 18 Pump 20 Washing Tower 61, 62, 63 Tube 64, 65 Annular groove 66, 67 Reversible valve M Motor-13-1-(Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm)
五、發明説明 原則上，讀等特对是朦於水溶液系統，例如自食品液 (foodstuff tiquids)中勝水移除，係可自美筚，A 4 〇〇4 886， 美國-A 4 316 368，美國，A 4 430 ί〇4 及美國-A 4 459 144 中所獲知β此外，項於在數階段中砘化化學品<懸浮結晶 法業已根據美國-Α4 787鉍5而輕提出。 全部譎等方垮之共同特徵係在於其具有結晶器（用於多级 結晶法之例手中之务階段），其中讀晶體係藉由將熱去除 而凍结出；再結晶器，其中大的晶體係籍由，失小的晶體 而成長出；以及濾器，其中將該晶體自母液中分離出。至 少’在最終階段之濾ϋ係採用洗涤塔之形式。 珠滌塔之功能係在艇獲自母液中之純的結晶相完全分離 淑。於此例中，將晶體漿體(crystal办jfjy)從底下遂料至塔 中，笨藉由、篩板形式之模具緊密之，母波向下流經篩板， 並在_板上面形成緊密之晶體塊(饥yStalbl〇pk)。於禹體塊 之上，將自母液釋放虚之蠤體，藉由刮刀自該晶艟塊上到 出，經蝝牝聲排肖。於此例中，'晶體塊柔已熔佴晷體之液 態壓力係維搏在f定的程度，像得少暈液體得以通堤晶體 塊’以便清洗出黏著之母液。經分離所得冬結晶相純束， 大多視晶體之熔溫與進料至洗滌塔之晶體槳罈之溫差两 定。結果，'該洗藤塔僅可皋進料之晶體懸浮液與已熔之純 相兩者在達溫差'5至最大1〇 <>c下操作才具有優勢。 L______ 4 t ( cns ) aammt (21^7^17 五、發明説明（ A7 B7 另一亨面’有機化合物混合物係依照混合之比钶而幾得， 就其藉由結晶而完全可達分離而言，根辞液相菇線(Hquidus ciirve)，該舞晶懸浮液與蟓被分離之純的結化合物之熔溫 間有著相當大之溫差。 經濟部中央標準局員工消費合作社印製 雖然’在洗滌塔之前’於最終階段時，藉由多級結晶法可 能使蟲fe懸浮液之液相濃度增加至一定的程度，使得母液 所達之液相線溫度(lic]pjidus temperature)大鈞相應於起始混 合物冬液相線溫度，而按照裝嬙而言，道將引起相當、轾度 的費用’因而抵>肖懸浮結.晶诀於靜態法之優勢。 通常有機化合物於彼此間產生非常低之固相溶解摩，固此 為夭上單一措段懸泮鲒晶係較適合於分離9 本梦叼之目的係在提供一種方法，其於懸浮結晶中使所需 之結晶階段數目可經減少。 本發明提梃一種用於轉由單一或多鍊懸浮結晶而將有機化 合物分離之方法，其中各階段係包含結毳赛，視禽要而有 用於貞晶體漿艟中分離液相之再結晶器及濾玆，其中辦:濾 器中經分離得之液相歸返至相關之結晶階喪，膊晶體漿體 移轉至後續之階段或自最終階段進入洗務塔，以將母液完 拿分離、且自最初階段將耗乏欲結晶化合物之母液推出， 本紙張尺度適用中國國家標準（tNS ) A4規格（210X297公釐） -n^· 1^1 m - I (請先閎讀背面之注意事項再填寫本頁} -、可V. Description of the invention In principle, the reading pairs are in the aqueous solution system, such as the removal of water from foodstuff tiquids, which can be obtained from the United States, A 4 004 886, the United States-A 4 316 368 , United States, A 4 430 〇 04 and United States-A 4 459 144 β In addition, the item in several stages of the tritiated chemical < suspension crystallization method has been proposed based on the United States-A4 787 bismuth 5. The common feature of all the equivalents is that they have a crystallizer (used in the stage of multi-level crystallization), in which the crystal reading system is frozen out by removing heat; the recrystallizer, which is large The crystal system grows by losing small crystals; and a filter in which the crystals are separated from the mother liquor. At least ' the filter at the final stage is in the form of a washing tower. The function of the pearl polyester tower is to completely separate the pure crystalline phase obtained from the mother liquor in the boat. In this example, the crystal slurry (crystal jfjy) is fed from the bottom to the tower. The mold in the form of a sieve plate is tight, and the mother wave flows down through the sieve plate and forms a tight Crystal block (starved). On the Yu body block, the virtual carcass will be released from the mother liquor, and it will come out of the crystal bar with a spatula, and the sound will be wailed with a snoring sound. In this example, 'the liquid pressure of the crystal block is melted at a fixed level, so that the liquid can pass through the crystal block' to clean the adherent mother liquor. The pure bundle of winter crystal phase obtained after separation mostly depends on the melting temperature of the crystal and the temperature difference between the crystal paddle fed to the washing tower. As a result, 'the rattan washing tower can only be operated at a temperature difference between' 5 and a maximum of 10 < > c only when the crystal suspension and the molten pure phase which can be fed are operated. L______ 4 t (cns) aammt (21 ^ 7 ^ 17 V. Description of the invention (A7 B7 The other organic surface mixture of organic compounds is obtained in accordance with the mixing ratio 几, as far as it can be completely separated by crystallization The root liquid phase mushroom line (Hquidus ciirve), the dance crystal suspension and the melting temperature of the pure junction compound separated by a considerable temperature difference. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs At the final stage of the tower, the multi-stage crystallization method may increase the liquid phase concentration of the worm-fe suspension to a certain degree, so that the liquidus temperature (lic) pjidus temperature reached by the mother liquor corresponds to The initial liquidus liquidus temperature of the mixture, and according to the terms of the installation, the Tao will cause a considerable cost, so the cost is greater than that of Xiao Suspension Junction. Crystals have the advantage of static methods. Usually organic compounds produce very low levels between each other. The solid phase dissolves and rubs, so this is a single suspended crystal system suitable for separation. The purpose of this 9 nightmare is to provide a method that can reduce the number of required crystallization stages in suspension crystallization. The present invention provides梃 A method for separating organic compounds by single- or multi-chain suspension crystallization, in which each stage includes a scouring race, depending on the needs of the bird, a recrystallizer and a filter for separating the liquid phase in the crystal slurry In which: the separated liquid phase in the filter is returned to the relevant crystallization stage, and the crystal slurry is transferred to the subsequent stage or enters the washing tower from the final stage to separate the mother liquor and separate it from the original. At the stage, the mother liquor that is depleted of the compound to be crystallized will be introduced. The paper size applies the Chinese National Standard (tNS) A4 specification (210X297 mm) -n ^ · 1 ^ 1 m-I (Please read the precautions on the back before filling in this Page}-, may
五、發明説明（4 ) 經濟部中央標準局員工消費合作社印裝 起始化'合物混合物於最終階段之後.進料，其特徵在於來自 最終扁晶階段之晶、體漿體之母液’至少部份，將漸次與起 _域化合物混合物交換《 交換可於皇少雨階段下逐步發生。 較佳地，支換係以逐漸旗連續地，即，以恒定極小之步驟 在進行。此係可於雨面均具有篩形式之壁之流槽(fl〇w channel)中進行，其中起始化合物混合物自一邊淹入，經過 篩’而自其餘之一邊母液，經竭另篩而經排去。 根據特別較佳之具體實施例，流槽為具有環狀之流槽，而 其係藉由同心篩管,(sieve pipe)所形成a較佳之交換裝聋係 乌括三條琦心管(concfcntyiCpip4 ’兩條採用篩形式之内層 管。將自最終結晶階段出現之晶體漿液進料I外層管，並 將母液自最內膚管排出。 特別優越、之形式，係在於準備用於進料之起始化合物混合 物’且排出欲經藉由換向閥進行可交換之母液。依此法， 經過篩孔之流向可經換向並可有妓地避免任何的阻斷。 交換較佳則係依如此之方式來進行’以使運送晶體漿液之 母液與經結晶之化合物，即，將部份結晶相再熔解於母液 中’形成未飽和。未飽和較隹則係經選擇在於使2至5 % 6 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本買) -装. 訂 A7 '、 __ B7五、發明説明（5 ) 經濟部中央標隼局員工消費合作牡印製 之結禺相得以經丹熔解。此係可避免於交換裝置中產生晶 體結塊。 1單二階段結鬲法中r藉由耷換將排出之母液歸返至結晶 =6於多級結晶法中，蓉換母液較隹射係歸返至前一結晶 階段。而特別較佳者，孫於前一階段令使用相應交換之母 崎。 根據本發明之方绛較隹係於僅具一結蟲階段下進行< 特別較隹者，係將根據本發明之方法使用於異氧酸鹽美構 物今分離，特树是用於自含有>二異氧酸甲次苯醋及 2,4’-立苯甲烷二異氰酸酯之異構物混合物中，獲得純的 二異氰酸甲次苯靡及4，心二苯甲轉二異表酸酯。 ？ 經獲得之二真氱酸申吹苯酿係含有邠％ 2木TDI及2〇 % 2,6-TDi之異構物渌合物〇該混合物之液相線溫度為g 5 eC。純的2,4-TD,I之熔點為22 °C &依照不同的反應行為， 當於聚加成方法中使甩TDI以用於製造聚胺基_酸乙酯 時* 一方面使用純的異耠物2,4-1：〇1而另一方面則使甩65 至矽％ 2,4-Tbi和35至31 % 2,6_TDJ之異辦物潺合物。 含有65 % 2,6-yi^之異樽物混合物之液相線溫度约石3 °c。玛此單i階段懸浮結晶法之晶齄婕體真肴6S亡之溫 度。就於洗滌塔中對純的結晶，進行有效之分離時，則須 7 本紙張尺度適用中國囤家標準(CNS ) A4規格（2I〇x^^y (#先閲讀背面之注意事項再填寫本頁) 裝_ A7 ________ B7五、發明説明（6 ) 經濟部中央標準局員工消費合作社印製 勝於至少12 °c之溫度之蟲體懸浮液，進料至洗释4中以容 許純时2,4“TDI相之熔溫。容許有可泵混舍物之額外需求， 其較佳係具有不超過30 %豕晶艟含量，雨該濃度可僅藉由 接受非經濟上至少50 %結晶相之高再熔解或藉由多&結 晶，而將起始化合物混合物加入晶體锻辕。 於另一方面，由於根據本發明，蘀由與起始異構物馬合物 連續一逐漸地交換母液之結果，使得在依滅本方法時，僅 在接受2.5至5 %之有效再熔解速率下，其則可能容易地 提供必須之起始母液濃度及溫度以用於洗滌瑢。若所需之 產物係存於士4，TPI中，經耗乏而含有谷7 % 2,4-TPI之相 時’其足以用該母液與僅為部份之·起始異構物混合物交 換’且足以角晶體漿體與殘餘起碲莫構物混合物滗合。若 3有石7 % 2,4-Tl>i之產物為所需時，其則足以於兩嘴段中 進行起始異構物混合鉀與母磚之交換，其中將部份起始矣 構物漏合物與該晶體聚體連續混合，然、後並在殘餘起始異 構物混含物與晶體漿體於另容器中進行混合之前，將母 液以濾器排凼*藉由分離濾器或直接在洙滌塔中，將過量 母液自最終交換階槔排出。 本發明將根楗所附冬，圖示更烊細於底卞説明： 圖* 觀示根據本發响而具有二階挺交換之單一階巍 結晶法。 本紙張尺度適用家標準（CNS )八4麟（2 (請先聞讀背面之注意事項再填寫本頁j _裝- 、βτ 五、發明説明（ 圖2 A7 B7 顯示根據本發明而具有漸次交換之單—階段社 晶涤。 經濟部中央椁率局員工消費合作社印袋 圖3 顯示根據本發明之二階段結畢法。 圖4 顯不於兩階段中均含有每液之二階段結晶法。 圖5 顯亲根據本發明之轉j圭交換襄置。 圖1係以圖顯示結晶器1 ’其申經由冷卻夾套2，使熱自 位於該處之晶體懸浮、液中移除。冷卻爽套2係藉由冷;^單 元3冷卻。經由管線4將晶爨懸浮液進料至交換容器5， 其係作氣母液最初之交換階段經由警線6a將二部份之起 始化合物混合物’較佳約4040 %，進料至交換容器5。 藉由濾器7，經管線8使交換母琅歸返至，結晶器丨。經由 管線9自交換谷器5中將晶體躡浮液排出·，該懸浮液_之 母液較之經由管線4布離秤結晶容器之晶寧懸浮液，具有 較高A欲經結晶之牝合物濃度，流鏟管線8之質童辱綠控 ♦J，以使容易可1之晶體懸浮液出現於管線9中，即、，存 於管蜂9中之晶體懸浮液具有25-35 %之固體含暈。經由 官線細進科之趄始物質混合物，其係於待經管線4而與經 進料之邁體懸泳液混合後：，使得該混合物為稍微和眸 《溫度下進料。瘦由管，b，將起始化合物齡== 9 本紙張尺度，適财賴家襟準（CNS ) M规格（2iGX297公幻 ——1.—„—ύ裝— (請先閲讀背面之注意事項再填寫本頁λ 、βτ Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（8 ) 部份進料至混舍容器i〇中，南來自交換容器5之晶體懸淖 液亦經由管線9而進入其中？混合容器扮係伟為第二階段 中漸次母液交換0可於混合容器1〇之出口處提輪濾器★藉 此而將過量母液分離並歸返至結晶器1。於所顯示4真體 實施例中*滤器之功能係藉由洗務塔20所接任。經由管線 η及洗滌塔20中篩板13上面往復泵之空心軸，、將晶蹲懸 浮液進料至該洗滌塔中。往復泵ύ將篩板13週期性地往 上移動，使母液經由篩板13而流向下。由於篩板之#動， 則緊密之晶體塊可於篩板13上面形成。在晶讀塊上面，藉 由刮刀14將純蝻晶體刮離晶體塊，於熱交換翁15中至少 部份經熔化且於箭號17之方向幾由闕16而將成為純的可 結晶之化合物棑出。藉由作為用於經刮由晶體之輸送介質 之泵，將部份經熔化之純妁可結晶化合物歸返至洗滌塔 前端。藉由遶嗇調整閥16，使維持於洗滌礞前释之壓力得 以將部份純的可鱔晶化合物作為洗蘇液^來加壓’以對抗緊 密之晶體塊。 洗務塔中經分離得之毋液，經由管線19而歸返至結晶器i 中。將可結晶化合物中經耗乏之母液，經由攄器22及營線 幻而良結晶器中排出。根據圖！之裝置係適合幹自含有8〇 %2,4-TDI之起始真構物混令物中分離卑2,‘TE)I，並獲得 仍含有69%2,4-TDI之經耗乏異構物混合物〗如上所述。 於圖2中，圖1之交換容器5係争交換塔5所取代，以用 於連續漸次母液之交換。交換塔5則於底下有吏詳蜂之說 10 个雜錢通用中國國家標準（CNS) A4規格（2ι〇χ297公羞） I —| i . 裝 訂 I I. (請先閲讀背面之注意事項再填寫本頁)V. Description of the invention (4) The consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs prints the initial compound mixture after the final stage. The feed is characterized by the crystals from the final oblate stage and the mother liquor of the body slurry. In part, it will be gradually exchanged with a mixture of compounds from the domain, "The exchange can occur gradually in the stage of Huang Shaoyu. Preferably, the switching is performed continuously with a gradual flag, i.e. in a constant minimum step. This series can be carried out in a flow channel where the rain surface has a sieve-like wall, in which the starting compound mixture is flooded from one side, passed through the sieve, and from the other side of the mother liquor, after passing through another sieve. Exclude. According to a particularly preferred embodiment, the flow channel is a ring-shaped flow channel, which is formed by a concentric sieve pipe. A better exchange device is a deaf system consisting of three chi heart tubes (concfcntyiCpip4 'two The strip uses an inner tube in the form of a sieve. The crystal slurry appearing from the final crystallization stage is fed into the outer tube I and the mother liquor is discharged from the innermost skin tube. The form is particularly superior because it is prepared for the starting compound for feeding The mixture 'and the mother liquid to be exchanged through the reversing valve are discharged. In this way, the flow through the sieve can be reversed and any blocking can be avoided prostitution. The exchange is preferably in this way Perform 'to make the mother liquor carrying the crystal slurry and the crystallized compound, that is, to re-melt a part of the crystal phase in the mother liquor' to form an unsaturation. The unsaturation is selected to be 2 to 5% 6 paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this purchase)-Packing. Order A7 ', __ B7 V. Description of the invention (5) Employees of the Central Bureau of Standards, Ministry of Economic Affairs Consumer Cooperation The printed crust phase can be melted by Dan. This system can avoid the formation of crystal agglomeration in the exchange device. 1 In the single-stage and two-phase crust formation method, the discharged mother liquor is returned to the crystal by changing the crystal = 6 in multiple stages. In the crystallization method, the mother liquor of Rongchang is returned to the previous crystallization stage compared with the projectile system. However, particularly preferably, Sun orders the corresponding exchanged mother saki in the previous stage. In the first stage of the infestation stage, the "special comparison" is to use the method according to the present invention for the separation of the isoformate aesthetic structure, and the special tree is used for self-contained > In the mixture of isomers of 2,4'-phenylmethane diisocyanate, pure diisocyanate diisocyanate and 4,4-dibenzoyl diisoepiate were obtained. Shenfeng benzene brewing system contains 邠% 2 wood TDI and 20% 2,6-TDi isomer admixture. The liquidus temperature of this mixture is g 5 eC. Pure 2,4-TD, I Melting point is 22 ° C & According to different reaction behaviors, when TDI is used in the polyaddition method for the production of polyurethane_acid ethyl ester * On the one hand, pure isocyanate 2 is used , 4-1: 〇1, on the other hand, it is a mixture of 65 to silicon% 2,4-Tbi and 35 to 31% 2,6_TDJ. It contains 65% 2,6-yi ^ The liquidus temperature of the bottle mixture is about 3 ° c. This is the temperature at which the crystallized body of the single-stage suspension crystallization method is 6S. When the pure crystals are effectively separated in the washing tower, It is required that 7 paper sizes apply to the Chinese Standard for Storehouse Standards (CNS) A4 (2I〇x ^^ y (#Please read the notes on the back before filling this page). _ A7 ________ B7 V. Description of Invention (6) Ministry of Economy The Central Bureau of Standards Consumer Co-operative Society prints a worm suspension that is better than a temperature of at least 12 ° C and feeds it into Wash 4 to allow a melting temperature of pure 2,4 "TDI phase. Allowing additional requirements for pumpable mixes, it is preferred to have a content of no more than 30% osmium, which can be remelted only by accepting a non-economically high crystalline phase of at least 50% or by multi-amplification Crystallize while adding the starting compound mixture to the crystal forging. On the other hand, according to the present invention, as a result of the continuous and gradual exchange of the mother liquor with the starting isoform horse hydrate, the effective remelting rate of 2.5 to 5% is only accepted when the method is destroyed. Next, it may easily provide the necessary initial mother liquor concentration and temperature for washing the mash. If the desired product is stored in Shi 4, TPI, when depleted, it contains 7% of the 2,4-TPI phase, which is sufficient to exchange the mother liquor with only a portion of the starting isomer mixture 'And it is sufficient that the horn crystal slurry is combined with the residual tellurium structure mixture. If the product of 3 yoke 7% 2,4-Tl> i is required, it is sufficient to exchange the starting isomer mixed potassium with the mother brick in the two mouth sections, in which a part of the starting structure The material leakage compound is continuously mixed with the crystal aggregate, and then, before the residual starting isomer mixture and the crystal slurry are mixed in another container, the mother liquor is drained through a filter * by a separation filter or Directly in the scrubber column, excess mother liquor is discharged from the final exchange stage. In the present invention, the winter season is attached, and the diagram is more detailed than the bottom description: Figure * Views a single-stage crystallization method with a second-order stiffness exchange according to the present invention. This paper size applies home standards (CNS) 8 4 Lin (2 (please read the precautions on the back before filling in this page j_ 装-, βτ 5. Description of the invention (Figure 2 A7 B7 shows a gradual exchange according to the present invention) Single-phase company crystal polyester. Figure 3 shows the two-phase completion method according to the present invention. Figure 3 shows the two-phase crystallization method of each liquid in the two phases. Fig. 5 shows the transformation of the progenitor according to the present invention. Fig. 1 is a diagram showing the crystallizer 1 'which passes through the cooling jacket 2 so that heat is suspended from the crystals located there and removed from the liquid. Unit 2 is cooled by cold; unit 3. The crystal hydrazone suspension is fed to exchange vessel 5 via line 4, which is the initial exchange stage of the gas mother liquor. The two parts of the starting compound mixture are mixed via police line 6a ' Preferably, about 4040% is fed to the exchange vessel 5. The filter 7 is returned to the crystal exchange via the line 8 to the crystallizer 丨. The crystal floated liquid is discharged from the exchange valley 5 via the line 9 ·, The mother liquor of this suspension_ is compared to Jing Ning Floating liquid, with a higher concentration of the compound to be crystallized, and the quality of flow line 8 is controlled in order to make the crystal suspension of easy 1 appear in line 9, that is, stored in the tube The crystal suspension in the bee 9 has a solid content of 25-35%. The original material mixture is finely processed through the official line, which is mixed with the feeding body suspension liquid after passing through line 4: , Make the mixture a little bit below the temperature of the feed. Thin tube, b, the starting compound age == 9 paper size, suitable for financial and household standards (CNS) M specifications (2iGX297 public magic-1 .— „— ύ 装 — (Please read the notes on the back before filling in this page λ, βτ Α7 Β7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) Part of the material is fed to the mixed container i 〇 In the south, the crystal suspension liquid from the exchange container 5 also enters it through the line 9? The mixing container looks like a gradual mother liquid exchange in the second stage. The wheel filter can be lifted at the exit of the mixing container 10. Instead, the excess mother liquor is separated and returned to the crystallizer 1. In the real example shown 4 * filter The function is taken over by the washing tower 20. Through the line η and the hollow shaft of the reciprocating pump above the sieve plate 13 in the washing tower 20, the crystal squatting suspension is fed into the washing tower. The reciprocating pump will sieve the plate 13 periodically moves upwards, so that the mother liquor flows down through the sieve plate 13. As the sieve plate moves, a tight crystal block can be formed on the sieve plate 13. Above the crystal reading block, the pure crystal block is scraped by the scraper 14. The rubidium crystal is scraped away from the crystal block, and at least part of it is melted in the heat exchange member 15 and will be made into pure crystallizable compound by the rubidium 16 in the direction of the arrow 17. It is used as a scraper to crystallize the crystal. The pump that transports the medium returns part of the molten pure crystallizable compound to the front of the washing tower. By bypassing the adjustment valve 16 to maintain the pressure released before the washing, the partially pure crystallizable compound can be recovered. The compound is pressurized as an effervescent fluid to combat tight crystals. The separated liquid in the washing tower is returned to the crystallizer i through line 19. The depleted mother liquor of the crystallizable compound is discharged through the crystallizer 22 and the crystal line molder. According to the picture! The device is suitable for the separation of 2, 'TE) I from a mixture of starting true structures containing 80% 2,4-TDI, and to obtain the depleted difference which still contains 69% 2,4-TDI. The structure mixture is as described above. In Fig. 2, the exchange vessel 5 of Fig. 1 is replaced by an exchange tower 5 for continuous progressive mother liquor exchange. The exchange tower 5 has a detailed description of 10 miscellaneous coins at the bottom. The general Chinese National Standard (CNS) A4 specification (2ι〇χ297 public shame) I — | i. Binding I I. (Please read the precautions on the back before (Fill in this page)
經濟部中央標準局員工消費合作社印製 艮據圖2所顯示之裝置’係適合於自含有80%2,4-Tm 65，始異構鱗錢巾麟2,4·Τ〇Ι <軸时獲得舍有 之Μ耗乏桌構物遇合物(經由管線21移除）。 全部起姶異構物渑合物較佳係經管線6a而進料至爻換塔 概據圖3之二階段結晶法中’自交換塔5中流出之經交換 母液，係經由管線8歸返至第一階段①，梁與最初階段中 ，開結晶器31之晶體懸浮液於混合容器4〇中混合。於濾 中，過董母液（考慮可泵性）經由管線41自雖開^ 合各器40之母夜中分雜並歸返至結晶器31。 根據圖3之方法係特別適合於二笨甲烷二異氰酸酯 昇構物之分離。由於該生產方法，使得_1係以經含有 如％ 4+MDI及1〇 % 2,4，am之起始異構物混舍物而獲 得，其中仍出现少量之2>2，-MDl。起始異構物混合物之赛 相線溫度約筇純的4,4，-MDI具有4(TC之熔溫。欲經 拂出且耗乏4,4t7MDi之異構物混合物仍有％重量％及13 °C液相1線溫度之4,4'-MDI。因此，離開結晶器31之晶體 懸淨液其有18 °C之溫度P第二锆晶階段1係於幕度27 °C 下操作。此係對應於含有76 % 4,4-MDI之母液。經由管線 4將母液進鱗至交換塔5中。經由管線6將具有溫度4^1 且含有9〇 % 4,4’-MDI之起始異構物混合物進枓至交換塔 5。經由管線8將含有76%4,4'-MDI之母液流出。經由管 11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I ---1.--_- —ip 裝------訂 J ― (請先閲讀背面之注意事項再填寫本k ) 經濟部中央標準局員工消費合作社印製 A7 --—-----—_____B7 五、發明説明（10 ) v二^讀塔5之晶體料液具有相應於液相綠溫康 32且* 80 V。4,4’-MDI之母液6對於經由管線6進料之 每1θ〇份起始異構物混合物，有77歸純的4,4，-MDI將經 由g線I7拂出，以及η2份仍含有％%工之莫構 祕合物f騎魏51棑t齡㈣管❹及管線49 之質量流置’可於管線4、9&u帽得3G%_含臺σ 最初階段離騎㈣31之晶雜料之赚含量係僅23 %。根據圖4之本發明具體實施例中，交換塔5及樣各 別於一階段I及II中所採供。結果，於混合容器4〇及管線 41中之母液濃度可能铖增加’俾便管線34及4中之固體 令羞亦能增加即，Μ切之異構分離柄間’質量瑪量被減 少。此外；根據圖4斯含之裝置，係可能於乒階段中分離 出化合物之鸪合物*其中較之於異構分離中所述而有 欲經排出且甚聋較大耗乏之混合物可經由管線51 _產 生。 虛線6b、&友49係代表僅有較少量之質量流量，其係用 於禅制該方法或用於適合將該方法導引至欲經解決特定問 題'時之情沈。 厨5顯示母:液交換管5，其根據本發明係可經使用，該管 包+乓條同心管61、62及63，其中内層管61及62係搡 用籂管形式。來自於結晶器之晶體懸浮液係流過介於二篩 管61及科間之環狀槽細mjul取channel) 64 6將起始粪構物 η 本紙張尺度適用中國國家標準（CNS ) M規格（210X297公釐） ---.:Ί---.1 L--^裝--^-----訂 ·- (請先閲讀背面之注意事項再填寫本頁) B： gT视雜 五、發明說明（11 ) 福充 ij 混合物依箭號6之方向進料至外層環狀槽65，而該混合物 則經由篩管62進入環狀槽64。同時，強迫母液進入内層 篩管61並經由管線8而排出。通過篩管61及62之流向 係 可藉由同時可換向之閥66及67換向，俾使篩孔阻斷可經 週期性換向而減少，或可藉由管線6或8中所測得之壓力 變化而引發換向而使篩孔阻斷減少。於各例中藉由換向而 發生環狀槽中母液濃度之變化係可在各例中之下游混合容 器中被平均。 圖式中之標號具有下列意義： (請先閱讀背面之注意事項再填寫本頁) — 經濟部智慧財產局員工消費合作社印製 1，31 結晶器 2 冷卻夾套 3，33 冷卻單元 4, 6, 6a, 6b, 8, 9, 11, 17, 19, 21, 34, 41, 48,49, 51 管線 5, 35 交換容器 7, 22, 47 濾器 10，40 混合容器 12 往復泵 13 篩板 14 刮刀 -13 - 訂---------^ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 A7 iVi λ:：, S8* 9* 2¾ B7 Ui本年月Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The device shown in Figure 2 is suitable for self-contained 80% 2,4-Tm 65, which is a heterogeneous scale money towel 2,4 · T〇1 < axis Obtained M depleted table structure compound (removed via line 21). All the isomers are preferably fed to the conversion tower via line 6a. According to the two-stage crystallization method of FIG. 3, the exchanged mother liquor flowing out of the exchange tower 5 is returned via line 8. To the first stage ①, the beam and the crystal suspension of the open crystallizer 31 in the initial stage are mixed in a mixing container 40. In the filtration, the mother liquor (considering pumpability) is separated from the mother's night of each container 40 through the line 41 and returned to the crystallizer 31. The method according to Fig. 3 is particularly suitable for the separation of dibenzyl methane diisocyanate ascites. Due to this production method, _1 was obtained by a mixture of starting isomers containing, for example,% 4 + MDI and 10% 2,4, am, in which a small amount of 2 > 2, -MD1 still appeared. The phase line temperature of the starting isomer mixture is about 筇 pure 4,4, -MDI has a melting temperature of 4 ° C. The isomer mixture that is to be blown out and consumes 4,4t7MDi still has% by weight and 13,4'-MDI of liquid phase 1 line temperature at 13 ° C. Therefore, the crystal suspension leaving crystallizer 31 has a temperature of 18 ° C. The second zirconium crystal phase 1 is operated at 27 ° C. This corresponds to a mother liquor containing 76% 4,4-MDI. The mother liquor is fed into the exchange tower 5 via line 4. A liquid having a temperature of 4 ^ 1 and containing 90% 4,4'-MDI is passed through line 6. The starting isomer mixture enters the exchange column 5. The mother liquor containing 76% 4,4'-MDI flows out through the line 8. Through the tube 11, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) I --- 1 .--_- --ip equipment ------ order J ― (Please read the notes on the back before filling in this k) A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ----- ----—_____ B7 V. Description of the invention (10) v. The crystal material liquid of the reading tower 5 has a liquid phase corresponding to the liquid green Wen Kang 32 and * 80 V. The mother liquid 6 of 4,4'-MDI is passed through the pipeline 6 Each 1θ0 starting isomer mixture There are 77 purified 4,4, -MDI will be brushed out through the g-line I7, and η2 parts still contain %% of the non-structural compound fqiwei 51 棑 t age ㈣ pipe and the mass flow of line 49 '3G% can be obtained in pipelines 4, 9 & u caps. The initial content of the crystalline debris from Ride 31 is only 23% in the initial stage. According to the specific embodiment of the present invention shown in Figure 4, the exchange tower 5 and the sample Separate from the supply in Phase I and II. As a result, the concentration of the mother liquor in the mixing container 40 and the pipeline 41 may increase, and the solids in the pipelines 34 and 4 may also increase, that is, the M cut The mass mass of heterogeneous separations is reduced. In addition, according to the device shown in Figure 4, it is possible to separate compounds of compounds in the ping phase *, which is more desirable than that described in heterogeneous separations. The depleted and relatively depleted mixture can be generated via line 51 _. The dotted line 6b, & You 49 represents only a small amount of mass flow, which is used to meditate the method or to be suitable for the method Lead to the feelings of time when you want to solve a specific problem. Kitchen 5 shows a mother: a liquid exchange tube 5, which can be used according to the present invention, the tube package + pong Concentric tubes 61, 62, and 63, of which inner tubes 61 and 62 are in the form of concrete tubes. Crystal suspensions from the crystallizer flow through a circular groove between the two sieve tubes 61 and the fine mjul to obtain the channel.) 64 6 The starting fecal matter η This paper size applies the Chinese National Standard (CNS) M specification (210X297 mm) ---.:Ί---.1 L-^ pack-^ ----- Order ·-(Please read the precautions on the back before filling in this page) B: gT depending on miscellaneous 5. Description of the invention (11) Fuchong ij mixture is fed into the outer ring groove 65 in the direction of arrow 6, and the mixture It then enters the annular groove 64 through the screen tube 62. At the same time, the mother liquor is forced into the inner screen tube 61 and discharged through the line 8. The flow direction through the sieve tubes 61 and 62 can be reversed by valves 66 and 67, which can be reversible at the same time, so that the sieve block can be reduced by periodic reversal, or can be measured by line 6 or 8. The resulting pressure change causes commutation and reduces screen blockage. In each case, the change in the concentration of the mother liquor in the annular tank by reversal can be averaged in the downstream mixing container in each case. The labels in the diagram have the following meanings: (Please read the precautions on the back before filling out this page) — printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1, 31 mold 2 cooling jacket 3, 33 cooling unit 4, 6 , 6a, 6b, 8, 9, 11, 17, 19, 21, 34, 41, 48, 49, 51 pipeline 5, 35 exchange container 7, 22, 47 filter 10, 40 mixing container 12 reciprocating pump 13 sieve plate 14 Squeegee-13-Order --------- ^ This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by A7 iVi λ :: ,, S8 * 9 * 2¾ B7 Ui
I ' l7：J " ......... Vi-..'·;; ------- 五、發明說明（） 15 熱交換器 16 閥 17 箭號 18 泵 20 洗滌塔 61, 62，63 管 64，65 環狀槽 66,67 可換向之閥 Μ 馬達 -13-1 - (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）I 'l7: J " ......... Vi-..' · ;; ------- V. Description of the invention () 15 Heat exchanger 16 Valve 17 Arrow 18 Pump 20 Washing Tower 61, 62, 63 Tube 64, 65 Annular groove 66, 67 Reversible valve M Motor-13-1-(Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm)